Meta-phenylenediamines, process for preparation thereof, intermediate compounds and use of these meta-phenylenediamines as couplers for the oxidation dyeing of keratinous fibres and especially human hair

Abstract

New meta-phenylenediamines, process for preparation thereof, intermediate compounds and use of these metaphenylenediamines as couplers for the oxidation dyeing of keratinous fibres and especially human hair. The invention relates to the compounds of the formula: <IMAGE> (I) in which R1 and R2 denote, independently of one another, a hydrogen atom, a C1-C4 alkyl radical or a C2-C3 mono- or polyhydroxyalkyl radical, Z and Z' denote, independently of one another, a C1-C4 alkyl or C2-C4 hydroxyalkyl radical, with the proviso that, when R1 and R2 simultaneously denote a hydrogen atom, Z and Z' do not simultaneously denote a methyl radical, and to their addition salts with an acid, to a process for preparation thereof and also to their use, by way of couplers, in an aqueous vehicle, in combination with at least one oxidation dye percursor of the para type, for the dyeing of human hair. The invention also relates to the intermediate compounds of the formula: <IMAGE> (XI) in which R' denotes a hydrogen atom, a C1-C4 alkyl radical, a C2 or C3 mono- or polyhydroxyalkyl radical, or an acetyl or beta -chloethoxycarbonyl radical, and z and z' denote, independently of one another, a C1-C4 alkyl radical.

We claim: 
     
       1. A hair dye composition comprising in a cosmetically acceptable aqueous vehicle, 0.05 to 3.5 weight percent of at least one compound, as a coupler, having the formula ##STR23## wherein R 1  and R 2 , each independently , represent hydrogen, alkyl having 1-4 carbon atoms, monohydroxyalkyl having 2-3 carbon atoms or polyhydroxyalkyl having 2-3 carbon atoms, Z and Z', each independently, represent alkyl having 1-4 carbon atoms or hydroxyalkyl having 2-4 carbon atoms, with the proviso that, when R 1  and R 2  simultaneously represent hydrogen, Z and Z' do not simultaneously represent methyl, and   the acid addition salt thereof,   in combination with at least one oxidation dye precursor of the para type in an amount effective to dye said hair.   
     
     
       2. The hair dye composition of claim 1 wherein said oxidation dye precursor of the para type is selected from the group consisting of a para-phenylenediamine, a para-aminophenol, a heterocyclic para compound and a mixture thereof. 
     
     
       3. The hair dye composition of claim 2 wherein said para-phenylenediamine has the formula ##STR24## wherein R 1 , R 2  and R 3 , each independently represent hydrogen, halogen, alkyl having 1-4 carbon atoms or alkoxy having 1-4 carbon atoms, R 4  and R 5 , each independently, represent hydrogen, alkyl having 1-4 carbon atoms, hydroxyalkyl having 1-4 carbon atoms, alkoxyalkyl wherein the alkoxy moiety has 1-4 carbon atoms and the alkyl moiety has 1-4 carbon atoms, carbamylalkyl wherein the alkyl moiety has 1-4 carbon atoms, mesylaminoalkyl wherein the alkyl moiety has 1-4 carbon atoms, acetylaminoalkyl wherein the alkyl moiety has 1-4 carbon atoms, ureidoalkyl wherein the alkyl moiety has 1-4 carbon atoms, carbethoxyaminoalkyl wherein the alkyl moiety has 1-4 carbon atoms, piperidinoalkyl wherein the alkyl moiety has 1-4 carbon atoms or morpholinoalkyl wherein the alkyl moiety has 1-4 carbon atoms, or   R 4  and R 5 , together with the nitrogen atom to which they are attached, form a piperidino or morpholino heterocycle,   with the proviso that R 1  and R 3  represent hydrogen when R 4  and R 5  are other than hydrogen, or   the salt of said compound of formula (XII).   
     
     
       4. The hair dye composition of claim 3 wherein said para-phenylenediamine is selected from the group consisting of p-phenylenediamine,   p-tolylenediamine,   methoxy-para-phenylenediamine,   chloro-para-phenylenediamine,   
     
     
       2. 6-dimethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine,   2-methyl-5-methoxy-p-phenylenediamine,   2,6-dimethyl-5-methoxy-p-phenylenediamine,   N,N-dimethyl-p-phenylenediamine,   3-methyl-4-amino-N,N-diethylaniline,   N,N-bis (β-hydroxyethyl)-p-phenylenediamine,   3-methyl-4-amino-N,N-bis (β-hydroxyethyl) aniline,   3-chloro-4-amino-N,N-bis (β-hydroxyethyl) aniline,   4-amino-N-ethyl-N-(carbamylmethyl) aniline,   3-methyl-4-amino-N-ethyl-N-(carbamylmethyl) aniline,   4-amino-N-ethyl-N-(β-piperidinoethyl) aniline,   3-methyl-4-amino-N-ethyl-N-(β-piperidinoethyl) aniline,   4-amino-N-ethyl-N-(β-morpholinoethyl) aniline,   3-methyl-4-amino-N-ethyl-N-(βmorpholinoethyl) aniline,   4-amino-N-ethyl-N-(β-acetylaminoethyl) aniline,   4-amino-N-(β-methoxyethyl) aniline,   3-methyl-4-amino-N-ethyl-N-(β-acetylaminoethyl) aniline,   4-amino-N-ethyl-N-(β-mesylaminoethyl) aniline,   3-methyl-4-amino-N-ethyl-N-(βmesylaminoethyl) aniline,   4-amino-N-ethyl-N-(β-sulphoethyl) aniline,   3-methyl-4-amino-N-ethyl-N-(β-sulphoethyl) aniline,   N-(4-aminophenyl) morpholine,   N-(4-aminophenyl) piperidine,   
     
     
       2. 3-dimethyl-p-phenylenediamine and isopropyl-p-phenylenediamine,   said para-phenylenediamine being in free base or cosmetically acceptable salt form.   
     
     
       5. The hair dye composition of claim 2 wherein said para-aminophenol is selected from the group consisting of p-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-(β-hydroxyethyl)-4-aminophenol, 2-methoxy-4-aminophenol and 3-methoxy-4-aminophenol. 
     
     
       6. The hair dye composition of claim 2 wherein said heterocyclic para compound is selected from the group consisting of 2,5-diaminopyridine, 2-hydroxy-5-aminopyridine and tetraaminopyrimidine. 
     
     
       7. The hair dye composition of claim 1 which contains, in addition to the coupler of formula (I) another coupler selected from the group consisting of a meta-diphenol, a meta-aminophenol, a meta-phenylenediamine, a meta-acylaminophenol, a meta-ureidophenol, a meta-carbalkoxyaminophenol, α-naphthol, a β-keto compound and a pyrazolone. 
     
     
       8. The hair dye composition of claim 1 wherein said oxidation dye precursor of the para type is present in an amount ranging from 0.1 to 7 percent by weight based on the total weight of said composition. 
     
     
       9. The hair dye composition of claim 1 which also contains a dye precursor of the ortho type selected from the group consisting of an ortho-aminophenol, an orthophenylenediamine and an ortho-diphenol. 
     
     
       10. The hair dye composition of claim 1 which also contains a direct dye selected from the group consisting of an azo dye, an anthraquinone dye and a nitrobenzene dye. 
     
     
       11. The hair dye composition of claim 1 having a pH ranging from 8 to 11. 
     
     
       12. The hair dye composition of claim 1 having a pH ranging from 9 to 11. 
     
     
       13. The hair dye composition of claim 1 which also contains an organic solvent present in an amount ranging from 1 to 40 percent by weight based on the total weight of said composition, said organic solvent being selected from the group consisting of a lower alkanol, glycerol, a glycol, a glycol ether and a mixture thereof. 
     
     
       14. The hair dye composition of claim 1 which also contains at least one anionic, cationic, nonionic or amphoteric surfactant, or a mixture thereof, in an amount ranging from 0.5 to 40 percent by weight based on the total weight of said composition. 
     
     
       15. The hair dye composition of claim 1 which also includes at least one cosmetic adjuvant selected from a thickener, an antioxidant, a penetrating agent, a sequestering agent, a buffer, a perfume, an alkalinizing agent and a propellant. 
     
     
       16. A process for dyeing hair comprising (a) admixing at the time of use the hair dye composition of claim 1 with an oxidizing solution in an amount effective to develop the oxidation dye precursor,   (b) applying the mixture obtained in step (a) to the hair,   (c) permitting said mixture to remain on the hair for a period of time ranging from 10 to 40 minutes,   (d) rinsing the hair,   (e) shampooing the hair,   (f) rinsing the shampooed hair with water, and   (g) drying the hair.   
     
     
       17. A process for dyeing hair comprising (a) in a first stage, applying to the hair an oxidation precursor of the para type selected from the group consisting of a para-phenylenediamine, a para-aminophenol, a heterocyclic para compound and a mixture thereof,   (b) in a second stage, applying to the hair treated in said first stage at least one coupler compound having the formula ##STR25##  wherein R 1  and R 2 , each independently, represent hydrogen, alkyl having 1-4 carbon atoms, monohydroxyalkyl having 2-3 carbon atoms or polyhydroxyalkyl having 2-3 carbon atoms,   Z and Z', each independently, represent alkyl having 1-4 carbon atoms or hydroxyalkyl having 2-4 carbon atoms, with the proviso that, when R 1  and R 2  simultaneously represent hydrogen, Z and Z' do not simultaneously represent methyl, or   the acid addition salt thereof, together with an oxidizing agent, or alternatively   in a third stage, applying said oxidizing agent separately to said hair treated with said coupler compound of formula (I) in said second stage,   (c) permitting said oxidation precursor of the para type, said coupler compound and said oxidizing agent previously applied to the hair to remain on the hair for a period of time ranging from 10 to 40 minutes,   (d) rinsing the hair,   (e) shampooing the hair,   (f) rinsing the shampooed hair, and   (g) drying the hair.